Light-sensitive color-photographic emulsions

ABSTRACT

A LIGHT-SENSITIVE COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH COMPRISES A COUPLER OF THE GENERAL FORMULA   R1-CH(-COO-R2)-CO-NH-(X)N-B   WHEREIN R1 REPRESENTS AN ALIPHATIC HYDROCARBON RADICAL HAVING 8-20 CARBON ATOMS, R2 REPRESENTS HYDROGEN OR A LOWER ALKYL GROUP, B REPRESENTS YELLOW OR MAGENTA COUPLER RESIDUE, X REPRESENTS A RADICAL CONNECTING B AND   R1-CH(-COO-R2)-CO-NH-   N IS 0 OR 1.

United States Patent Clfice 3,694,214 Patented Sept. 26, 1972 3,694,214 LIGHT-SENSITIVE COLOR-PHOTOGRAPHIC EMULSIONS Masakumi Iwama, Isaburo Inoue, Teruo Hanzawa, Kenro Sakamoto, and Takaya Endo, Tokyo, Japan, assignors to Komishiroku Photo Industry Co., Ltd.

No Drawing. Continuation-impart of abandoned application Ser. No. 778,774, Nov. 25, 1968. This application Oct. 14, 1970, Ser. No. 80,749

Int. Cl. G03c 1/40 US. Cl. 96-100 7 Claims This application is a continuation-in-part of application Ser. No. 778,774, filed Nov. 25, 1968, now abandoned.

This invention relates to a light-sensitive silver halide color-photographic emulsion. More particularly, the present invention relates to a light-sensitive silver halide color-photographic emulsion containing, as a protected coupler or alkali-soluble coupler, a novel coupler compound of the general formula wherein R is an aliphatic hydrocarbon radical of 8 to 20 carbon atoms; R is hydrogen or a lower alkyl radical; B is a radical which couples with the oxidation product formed during color development to form a yellow or magenta color; X is a group capable of bonding the B group with a group of 000R: and n is or 1.

In order to be usable for commercial purposes, a protected coupler is required, in general, to satisfy the following conditions:

(1) The coupler should be prepared in high purity according to a simple synthetic process from readily available inexpensive materials.

(2) The coupler and a dye formed by color development should be well soluble in a high boiling solvent, such as tricresyl phosphate, dibutyl phthalate, etc., to give a high concentration solution.

(3) The coupler should have no detrimental effects, such fogging, desensitization, etc., on a silver halide emulsion.

(4) When the dispersion of the coupler in a silver halide emulsion is coated and dried on a support, the coupler should give a stable photographic layer which has not suffered from crystallization.

(5) The coupler should be favorable in color developing property, be excellent in spectral absorption characteristic of the resulting color-developed dye image and be fast to heat, light and humidity, and it should not cause staining of the unexposed area.

With an aim to satisfy the above requirements, many studies have been made and various couplers have been proposed hitherto. However, there has not been found a coupler which can satisfy the above requirements.

For example, the coupler disclosed in US. Pat. 2,875,- 057 which is represented by the formula mmGoomoounQ 0 on,

I a u COCHzCONH- COCuHzI H2CICNHC 0 CHzCHaN O: C4Ht is much more improved in solubility for high boiling solvents than the coupler of US. Pat. 2,875,057 but is very expensive because the lipophilic component thereof should be synthesized through several steps.

On the other hand, an alkali-soluble coupler also is required to satisfy, in addition to the before-mentioned requirements (1) to (5), with the good dissolution in aqueous alkali and the ready dispersion in photographic emulsions. In spite of keen studies in the prior art, there have never been found alkali-soluble couplers fully satisfactory to the above requirements.

For example, long chain alkyl succino-monoamide couplers disclosed in Japanese patent publication Nos. 18,735/64 and 12,836/66 can form a dye image excellent in light, humidity and heat fastness, but it is likely to be crystallized out from the emulsion or photographic coating due to its poor alkali solubility, thereby adversely affecting on transparency of unexposed area and colored dye image.

a-Sulfonated long chain fatty acid amide couplers disclosed in US. Pat. 2,829,975 and Japanese patent publication No. 18,333/ 63 is excellent in alkali solubility, is readily dispersible or miscible in emulsions and has little tendency to crystallize out. However, these couplers usually are very difficult in preparation and purification.

We have now found that a coupler of the aforementioned general formula is very useful as either of a protected coupler and an alkali-soluble coupler. The compounds used as couplers in the present invention can be easily prepared in a simple way by using long chain alkyl bromide and malonic acid ester as starting materials which are inexpensive and readily available. A light-sensitive color-photographic material which comprises a support and, coated thereon, a layer of the emulsion of the present invention can yield, through exposure to light and subsequent color development according to a usual method, a clear dye image with high color density. Transparency at unexposed area also is excellent. Further, the said color-photographic material is entirely free from fogging, desensitization and any other adverse effects on photographic properties.

When a compound of the aforementioned general formula is used as a protected coupler, a coupler dispersion having the high ratio of the coupler to the solvent amount is obtained because of high solubility of 4 the coupler in dibutyl phthalate, tricresyl phosphate, etc. Further, a photographic layer obtained from the said dispersion is stable and does not suffer from the crystallization of the said coupler.

When a compound of the aforementioned general formula is used as an alkali-soluble coupler, it can show better solubility than the known long chain alkyl succinmonoarnide coupler. The compound is readily miscible or dispersible in photographic emulsion and does not cause crystallization.

The remarkable improvement of a light-sensitive colorphotographic emulsion according to the present colorphotographic emulsion according to the present invention may be considered due to the existence of a carboxyl or lower alkoxy-carbonyl group at the a-position of a long chain fatty acid amide structure.

Now typical coupler compounds useful in the invention are listed hereunder.

TABLE-Continued C1a as-CH-C OHN-C ONH(IIJCH, 272 274 I coon 9 11-0111113-013-0 ONH- 4849 ooNH-( 1rr 10 10 n-CrcHas-(\1HO ONE-C} 7 108 c ONH-fi-(|)H,

N o=o 1 117-118 1) n-C H ;-(JH-O oNH--NH- :11,

n-C H 3-Cl3H-C ONE-QC o 0 OH I i N-NH H n-C H (IJHC ONH- CONH(l'T-C3H-N=N- -0 on,

00 OH N 0:0

Couplers usable in this invention are synthesized by the following method:

Diethyl alkylmalonate obtained by the reaction of a long-chain alkyl bromide with diethyl malonate is hydrolysed to the mono-ester and treated with thionyl chloride. The resulting acid chloride is condensed with an appropriate coupler intermediate having amino group to give an yellow or magenta coupler used in this invention.

PREPARATIVE EXAMPLE 1 Synthesis of diethyl n-hexadecylmalonate Into a 2 l. three-necked flask was charged a solution of 24.2 g. of metallic sodium in 480 ml. of ethyl alcohol, and 160 g. of diethyl malonate was added thereto. The mixture was stirred at 6070 C. for 15 minutes. 336

75 grams of diethyl malonate was added to the mixture under boiling, and the mixture was boiled with reflux for additional 2 hours. Thereafter, 450 ml. of the ethyl alcohol was removed by distillation, and the distillate was charged with water to separate an oil. The oil thus separated was 8 an ion exchange resin, Amberlite G 120, and then a column with Amberlite G 400. The solvent was removed by distillation under reduced pressure, and the residue was recrystallized from 500 ml. of n-hexane, whereby 30 g.

extracted with ether. The ethereal solution was Washed (yield 51%) of pale yellow powder having a melting with water, dried and then distilled to remove the ether. point of 77 -78 C.

'The residue was distilled under reduced pressure to obtain The exemplified couplers 1, 2, 5, 6, and are those 250 g. (yield: 65%) of a fraction having a boiling point which have been prepared by using intermediates and of 182-185 C. at 0.05 mm. Hg. acylating agents set forth in Table 1.

TABLE 1 Nitrogen Melting content point 01 (percent) coupler w Coupler Intermediate Acylating agent C.) Calcd Found 1 ot-(4-aminoberizoy1)Jrethoxycarbonyl-2-mothoxyacetaniiide a-Ethoxyearbonylmyristic acid chloride 77-78 4.74 4. 71 2-- a-(4-aminobenzoyl)-2-methoxyacetanilide a-Ethqxycarbonylstearie acid chloride 69 4.60 4.20 5.. 4-amin0benzoylacetonltrile.... a-Ethoxycarbonylcapric acid chloride", 93-96 7. 7.30 6 3-( i-aminophenyl)-pyrazoiinobenzimidazole a-EthoXs carbouylmyristio acid ohlorlde..-.- 160-161 10. 56 10.30 10 1-(2,4,6-trichiorophenyl)-3-(3-aminobenzamide)-li-pyrazoloue ot-Ethoxyearbonyistearic acid chloride 48-49 7.61 7.43

Elementary analysis-Cale. (percent): C, 71.83; H, BREPARATIVE EXAMPLE 5 Found (percent): 71'64; Synthesis of 1-(4-carboxyphenyl)-3-(4-ot-carboxystearoyl- PREPARATIVE EXAMPLE 2 aminobenzamide) -5-pyrazolone (exemplified coupler 9) Synthesis of monoethyl n-hex-adecylmalonate 25 36 grams of 1-(4-ethoxycarbonylphenyl)-3-(4-tz-ethoxy- A mixture comprising 200 g. of the diethyl ester obcaPEOXystgaroylammobenzamlde) py u tained by Preparative Example 1 and a solution of 29.5 g. 162 was added to a mlxmre comprlsmg 172 of potassium hydroxide in 610 ml. of ethyl alcohol was 1111- of ethyl alcohol 86 Q 20 pfimellt.of boiled for 5 hours. The alcohol was then removed by aqueous Sodium Y f 5011mm! and l'esultmg distillation, and the distillate was charged with 600 ml. mixture was stlrred t 45 for 10 mmules; of water and 50 ml. of concentrated hydrochloric acid. mlXtllfe Was dllllted W1th 500 l -P Water acldlfied The precipitate formed was collected by filtration, washed Wlth hydrochloflc acld- The Pfficlpltate deP01ted was Q with water, dried and recrystallized from n-hexane. There lectefi PY filtratlOP. washefi Wlth Water f 16(1- The 'f was Obtained 5 7% f white Powder having a precipitate was dissolved in 100 ml. of dimethylformamide melting point f 43 and diluted with methyl alcohol to deposit a coupler. The

Elementary c (percent); C, 7034; H, dilution was left to stand overnight, and the coupler was 1131' Found (Percent); C, 70 H, 5 collected by filtration, washed with methyl alcohol and dried. White powder having a decomposition temperature PREPARATTVE EXAMPLE 3 of 2s3-2s4 c. was obtained. The yield was 25 g. 77% Synthesis of athoxycarbonylstearic acid chlorid Elementary analysis.Calc. (percent): N, 8.64. Found 72 grams of the monoethyl ester synthesized according (Percent) to Preparative Example 2 was mixed with 71 g. of thionyl The exemplmed couplers and 13 are chloride, and the mixture was allowed to stand at ordinary pared rispectlvely from, starting mammals Set forth temperature overnight The thionyl chloride was then Table 2 in accordance with the procedure of Preparative distilled under reduced pressure, and the distillate was 45 Example used in the step of acylation which follows. TABLE 2 Using n-octylbromide or n-dodecylbromide in place of M m the n-hexadecylbro'mide and following the procedures of oint ii i teiit 253 x2231?) Preparative Examples 1 and 2, there were prepared long 0 1 St u t l 1 a m chain alkyl malonates having 8 and 12 carbon atoms, mm H at ngma era 80d mm respectively, which were then converted to corresponding 4 g g zgg ggggfigfigfgf gg' 180-181 449 acid chlorides according to the procedure of Preparative methoxyacetanilide.

E 16 3 7 l-phenyl -(a -ethoxycarb0uyl- 68-69 8. 65 8. 25

Xamp stearoylannno)5-pyrazolone.

8 i-[4-(4-tertlarybuty]phen0xy)-3- 267-269 5. 74 5. 56 Diester Monoester sulfophenyn.a. .ephoxycar B.P. P o. Yield M.P. Yield iiigii Alkyl 8 mm. Hg) (percent) 0-) (p 11 1-(2,4,6-trichlorophenyl)-3e[3-a- 107-108 7.91 7.69 n-ctHtt stem/3.0 65 9 itii iti aifiitigfigi ftigiligrli n-o nn'f 168169/2.0 4 92 12 1-(2,4,6-trichlorophenyl)-3-f4-(a- 117-118 7.51 7.40

ethoxycarbonyistearoylamino) lolly product 60 is e 1 1 J P i i 201 209 9 14 9 on u 0 l1 PREPARATIVE EXAMPLE 4 gg ggggfi i Synthesis of 0c (4 at ethoxycarbonyl myristoylaminobenzoyl) 5 ethoxycarbonyl 2 methoxy acetamide (exemplified coupler 1) PREPARATIVE EXAMPLE 6 Synthesis of l-(4-carboxyphenyl)-3-(4-iz-carboxystearoyl- To a mixture comprising 36 g. of ot-(4-aminobenzoyl)- 5-ethoxycarbonyl-2-methoxyacetanilde and 150 ml. of i g g }i pyridine was added 33 g. of ot-ethoxycarbonylmyristic one (exemp 1 e coup er acid chloride, and the mixture was heated at 9095 C. 10.0 grams of p-anisidine was diazotized with 120 ml. for 1 hour. The reaction mixture was diluted with water of water, 30 ml. of concentrated hydrochloric acid and to separate an oily product. The oily product was ex- 8.0 g. of sodium nitrite, and 400 ml. of ethyl alcohol was tracted with ethyl acetate, washed with water and dried. added thereto.

The ethyl acetate was removed by distillation, and the To a solution of 32.4 g. of the exemplified coupler 9 in residual oily product was dissolved in methyl alcohol and 324 m1. of pyridine was added at 510 C. the solution the solution was passed through a column packed with of diazonium salt prepared above. The mixture was stirred for 3 hours and then diluted with water and charged with 400 ml. of hydrochloric acid. The precipitate deposited was collected by filtration, washed with water and dried.

The precipitate thus obtained was dissolved in 100 ml.

\Addition of the coupler to a silver halide emulsion may be made according to a known method in a preferable amount of 15-100 g. per mol of the silver halide contained in said emulsion. The amount added is, however, variable of dimethylformamide and diluted with methyl alcohol, i h presentinventiom whereby an orange p p a was p p The p The light-sensitive color photographic material thus tate was collected by iiltration, washed with methyl alcoprepared is exposed to light and treated according to an and dneod to Qbtam oraPge POWder havmg meltmg ordinary developing treatment. Dye image obtainable Pomt of 244 The yleld was d from such color photographic material is improved in f l' 3% (Percent) 10 transparency and has desirable spectral absorption characi ifi f th I t t d teristics. Further, crystallization of coupler out of the e app i o ers Pm cc 6 c emulsion is remarkably inhibited, light scattering is not plers, a coupler is dlssolved 1n a high bollmg solvent such caused and max sad area is also im roved in mum as tricresyl phosphate, dibutyl phthalate, etc. alone or, if arenc p0 P necessary, in a mixture of the high boiling solvent with a 15 p l d 1 low boiling solvent such as ethyl acetate, butyl acetate, eve Opmg Solutions used thls mventlfm butyl propionate, etc. The resulting solution is dispersed in tam m the form 9 sulfates Sulfites hydrochlondes the an aqueous gelatin solution containing a surfactant by passfollowmg developmg agents: ing the mixture through a high speed rotary mixer or colloid mill. The resulting dispersion is added to a silver NN'dlethyl'p'phenylenedlamlPe halide photographic emulsion and the thus treated emull' 'F' Y Y -P-P sion is coated on a support such as film base, baryta paper, emdlamme etc. and dried. Alternatively, in the application of the cou- N-ethYLN- Y Y Y yl-P-phenylenediamine plers as alkali-soluble couplers, a coupler is dissolved in N-ethyl-N-hydroxyethyl-p-phenylenediamine an aqueous solution of a caustic alkali, alkali carbonate, N,N-diethyl-2-methyl-p-phenylenediamine etc. or in an aqueous alcohol solution. Addition of the coupler to a silver halide emulsion may be made after or Melting points of a-alkoxycarbonyl fatty acid amide before the pH adjustment of the coupler-alkali solution coupler used in this invention and a known coupler having with an aqueous citric acid solution. The treated emulclosely related structure to that of the above coupler are sion is then coated on a support and dried. compared in Tables 1 and 2 below.

TABLE 1 Comparison in melting point between the Coupler No. (2) and a known coupler similar thereto in structure Coupler Structural formula M.P. C.)

Coupler (No. 2) O CH; 67-69 C1|Hn(|3H-CONH--COCHzCONH- o o 0 CnHs Coupler disclosed in U.S.P. 2,875,057 126-127 tO H 0 CH CONfl- M3113 tCaHu ooomooun-Q TABLE 2 Comparison in melting point between the Coupler No. (9) and a known coupler similar thereto in structure Coupler Structural formula M.P. C.)

C p Ne 48-49 CuHaa- (1H- 0 O NH C o o 02H,

CONHC-CH| N C=O N l Cl[ -Cl 01 Coupler disclosed in U.S.P. 2,618,641

tc Hu OCH3CONH t t u As evident from the above tables, melting points of the couplers used in this invention are extremely lower than those of the known couplers and therefore crystallization out of the emulsion or coating is inhibited. Thus, stabilized light-sensitive photographic material is made according to this invention.

Solubility of couplers the used in this invention in a high boiling solvent is compared with that of known couplers having closely related structural formulas to those of the above couplers. Comparison is made by 10 measuring a temperature at which 1.0 g. of a coupler dissolves in 2.0 ml. of dibutyl phthalate and an amount (mL) of dibutyl phthalate required for dissolving 1.0 g. of a coupler at 45 C.

TABLE 3 Comparison in solubility between the Coupler No, (2) and a known coupler similar thereto in structure Amount of Temperadibutyl ture phthalate Coupler Structural formula 0.) (ml.)

Coupler No. (2) 0 CH: 43 2. 0

COOC H;

I tCiHu Coupler disclosed in U.S.P. 2, 875, 057.... 80 16. 0

tC H 0 CH CONH- OCH;

TABLE 4 Comparison in solubility between the Coupler No. (9) and a known coupler similar thereto in structure Amount of Temperadibutyl ture phthalate Coupler Structural formula 0,) 1,)

Coupler No. (9) 40 1. 5

Coupler disclosed in U.S.P. 2,618,641";

As obvious from the above test results, the couplers used in this invention are superior in the solubility in a high boiling solvent to the known couplers and therefore is dropped with starring at 2 2i1 C. until a turbid solution is formed with separation of precipitate. The pH value of the resulting solution is measured (pH at crystaluseful also as protected couplers. Moreover, the couplers 75 lization).

TABLE Comparison in solubility between the Coupler No. (6) and a known NN- yl-p-phenylenedlamme hydrochloride 2.5 coupler similar thereto in structure Sod1um sulfite (anhydrous) 2.0 pH at Sodium carbonate (monohydrate) 82.0 C I S t H 1 qryst 5 Potassium bromide 2.0

oup or true ura ormu a .zation Water to make p to 1000 m1. Coupler No. (6).... C;H3a-CHOONHC--OH 5.0

00011 :0 Whereafter, the photographic material is subjected to ordinary stopping, fixing and water washing for -15 10 minutes, and treated for 5 minutes with a bleaching solution having the following formulation:

G. Potassium ferricyanide 100 Potassium bromide 50 Coupler disclosed C1 H; -CH-CH1C0NHC-CH: as Water to make up to 1000 in Japanese Pat. Publn. No. 00011 N C=O After water washing for 5 minutes, the photographic 12836/66' material is treated for 5 minutes in the fixing bath com- I prising 2O G. Sodium thiosulfate (pentahydrate) 250 Water to make up to 1000 m1.

TABLE 6 Comparison in solubility between the Coupler No. (3) and a known coupler similar thereto in structure pH at crystal- Coupler Structural formula lization Coupler No. (3) 6. 5

C"H33(|1HCONH- OCH;

0 O OH O O C H; C O NH- I C O O H Coupler disclosed in Japanese Pat. Publn. No. 18735164... 0 CH; 6. 6

COOH

As obvious from the above test results, the couplers used in the present invention are superior also in the solubility in an aqueous alkali solution to the known couplers and therefore very useful as alkali-soluble couplers. Like as in the application as protected couplers, the couplers used in the present invention are free from crystallization out of the emulsion or coating in the application as alkali-soluble couplers. Moreover, the couplers increase color density and are satisfactorily usable in a reduced amount. Besides, the light-sensitive photographic material according to the present invention has photographic properties improved in color reproduction and graininess.

In order that the present invention may be well understood, the following examples are given by way of illustration only.

EXAMPLE 1 g. of the coupler No. (l) are dissolved in the mixture comprising 20 m1. of dibutyl phthalate and 60 ml. of butyl acetate at 80 C. Mixture of the resulting solution with 10 ml. of 10% aqueous solution of Alkanol B (alkylnaphthalenesulfonate of Du Font) and 200 ml. of 5% aqueous gelatin solution is passed through a colloid mill.

The dispersion obtained is added to 1 kg. of a high speed gelatino silver bromoiodide emulsion. The thus treated emulsion is coated on a film base and dried. The resulting light-sensitive photogrgaphic material is then exposed to light in an ordinary manner and treated at 20 C. for 10 minutes with a developing solution having the following formulation:

The light-sensitive photographic material thus treated is washed with water for 20-25 minutes and dried. Clear yellow dye image improved in spectral absorption characteristic and having the maximum absorption at 440 m is obtained.

A light-sensitive photographic material wherein the coupler No. (9) is dispersed in the emulsion in the same manner as above provides magenta dye image improved in spectral absorption characteristic and having the maximum absorption at 540 Ill 1., after light-exposure and subsequent color development elfected in the same manner as above.

EXAMPLE 2 10 .g. of the coupler No. (2) are dissolved in the mixture comprising 10 ml. of tricresyl phosphate and 30 ml. of butyl acetate at 60 C. Mixture of the resulting solution with 5 ml. of 10% aqueous solution of Alkanol B and 200 ml. of 5% aqueous gelatin solution is passed through a colloid mill.

The dispersion obtained is added to 500 g. of a gelatino silver bromoiodide emulsion. The thus treated emulsion is coated on a film base and dried. The resulting lightsensitive photographic material is then exposed to light and treated at 20 C. for 10 minutes with a developing solution having the following formulation:

G. Metol 3.0 Sodium sulfite (anhydrous) 60.0 Hydroquinone 6.0 Sodium carbonate (anhydrous) 50.0 Potassium bromide 1.0

Water to make up to 1000 ml.

15 After being subjected to ordinary stopping, hardening and water washing treatments, the photographic material is re-exposed to white light and treated at 20 C. for 12 minutes with a developing solution having the following formulation:

G. N,N-diethyl-p-phenylenediamine hydrochloride 5.0 Sodium sulfite (anhydrous) 2.0 Sodium carbonate (monohydrate) 82.0 Potassium bromide 1.0

Water to make up to 1000 ml.

EXAMPLE 3 10 g. of the coupler No. (6) are dissolved in 20 m1. of dibutyl phthalate at 50 C. Mixture of the resulting solution with ml. of aqueous solution of Alkanol B and 200 ml. of 5% aqueous gelatin solution is passed through a colloid mill several times. The resulting dispersion is added to 500 g. of a gelatino silver chlorobromide emulsion. The treated emulsion is coated on a baryta paper and dried.

The resulting light-sensitive photographic material is then exposed to light and treated at 20 C. for 10 minutes with a developing solution having the following formulation:

N ethyl N hydroxyethyl p phenylenediamine sulfate 2.5 Sodium sulfite (anhydrous) 2.0 Hydroxylamine hydrochloride 1.0

Sodium carbonate (monohydrate) 82.0 Potassium bromide 2.0 Water to make up to 1000 ml.

G. Disodium ethylenediaminotetraacetate 40.0 Ferric chloride 30.0 Sodium carbonate (monohydrate) 20.0 Potassium bromide 30.0

Sodium thiosulfate (pentahydrate) 200.0 Water to make up to 1000 ml.

The photographic material thus treated is subjected to water washing for 20 minutes and stabilizing for 2 minutes and then dried. Thus, magenta dye image having the maximum absorption at 535 m and improved in fastness to light, heat and humidity is obtained.

EXAMPLE 4 A solution of 10.0 g. of the coupler No. (8) in 60 ml. of N-potassium hydroxide aqueous solution is diluted with water to 200 ml. and adjusted with N-citric acid aqueous solution to pH 6.8. The resulting solution is added to 1 kg. of high speed gelatino silver bromoiodide emulsion. The treated emulsion is coated on a film base and dried. The resulting light-sensitive photographic material is then ex- 16 posed to light and treated at 20 C. for 10 minutes with a developing solution having the following formulation;

G. N,N-diethylamino-p-phenylenediamine sulfate 2.5 Sodium sulfite (anhydrous) 2.0 Sodium carbonate (monohydrate) 82.0 Potassium bromide 2.0

Water to make up to 1000 ml.

Being subjected to stopping and fixing in a usual manner, the photographic material thus treated is washed with -water for 10-15 minutes and then treated for 5 minutes with a bleaching solution having the following formulation:

G. Potassium ferricyanide 100.0 Potassium bromide 50.0

Water to make up to 1000 ml.

The resulting film is further washed with water for 10 minutes and fixed for 5 minutes in'the fixing bath comprising G. Sodium thiosulfate 250 Water to make up to 1000 ml.

After water washing and drying the film, magenta dye image having the maximum absorption at 535 mp. and improved in transparency is obtained.

From a light-sensitive photographic material wherein the coupler No. (3) is dispersed in the emulsion and the same treatments as above are effected, is obtained clear yellow dye image having the maximum absorption at 440 III 1..

EXAMPLE 5 A mixture of 10.0 g. of the coupler No. (9) and 30ml. of ethanol is dissolved in 10 m1. of 20% potassium hydroxide aqueous solution at 60 C. The resulting solution is diluted with water to 200 ml. and pH value is adjusted. This solution is added to 1 kg. of high speed gelatino silver bromoiodide emulsion and the resulting emulsion is coated on a support and dried.

The light-sensitive photographic material thus obtained is subjected to light-exposure and color development under the same conditions described in the Example 4. Thus, clear magenta dye image having the maximum absorption at 537 m is obtained.

What is claimed is:

1. A light-sensitive color photographic silver halide emulsion which comprises a coupler of the general formula R OI-IC0NH(X)n-B 00R: wherein H CHCONH n is 0 or 1. 2. A light-sensitive color photographic silver halide emulsion as claimed in the claim 1, wherein a coupler of the general formula is the compound of the following formula (I) C a n-cunu-ou-o o NH-ooomo ONH o 0 o (32H;

3. light-sensitive color photographic silver halide emulsion as claimed in the claim 1, wherein a coupler 17 18 of the general formula is the compound of the following of the general formula is the compound of the following formula formula nC H ;('}H-C O NH@ CH, C1o aa(|3 H-C ONE-Q COOH 5 COOCQH! COCHzCONH CONHC-( |,Hg

00H N 4. A light-sensitive color photographic silver halide emulsion as claimed in the claim 1, wherein a coupler 0f C1 the general formula is the compound of the following formula IlCuH:3CH-C ONH-C-C H: (E

\ 6. An emulsion according to claim 1 whereln X 1s a phenylene group.

7. An emulsion according to claim 6 wherein X is pphenylene or n-phenylene.

References Cited UNITED STATES PATENTS 2,875,057 2/1959 McCrossen et al 96-100 2,829,975 4/1958 Popeck et al. 9655 NORMAN G. TORCHIN, Primary Examiner E. C. KIMLIN, Assistant Examiner tCaHo 5. A light-sensitive color photographic silver halide US. Cl. X.R.

emulsion as claimed in the claim 1, wherein a coupler 96-55 

